Polymer materials are utilized in an increasing number of categories of products, such as components for cars, boats, airplanes, within the electronics industry and other advanced industry as well as in paints and other coatings, for special packaging etc. The uses of polymer materials in new categories of products are only limited by the product properties. It is thus a continuous need for development of polymer products with improved properties e.g. with respect to increased scratch resistance, improved weather resistance, increased UV resistance, increased chemical resistance and improved properties with respect to anti oxidation, anticorrosion etc.
In addition to pure polymer materials there has also been developed products based on materials that may be described as hybrids between inorganic and organic materials, which means that these materials are macro molecules that may have an inorganic core and organic branches.
Organic polymer molecules with branched structures have an enormous economical growth potential, particularly as components in new materials. So-called dendrimers are important examples of such polymer molecules with a perfectly branched structure as well as hyperbranched polymers with statistically progressive branching. Both dendrimers and hyperbranched polymers are denoted dendritic polymers. Dendritic (from Greec: “dendron”=tree) characterizes the principle of a progressive branching that is more or less perfect (G. R. Newkome, C. N. Moorefield, F. Vögtle, “Dendrimers and Dendrons: Concepts, Syntheses, Applications”, Wiley-VCH, Weinheim, (2001)). Formula 1 illustrates the principle difference between linear polymers and dendritic polymers (hyperbranched polymers and dendrimers).
FORMULA 1linear polymers Hyperbranched polymers dendrimersK germ (the beginning of the polymer molecule)L linear propagationD dendritic branchingT termination (the end of the polymer molecule)
Dendritic polymers are particularly interesting because the T units may carry functional groups and the density of available functional groups per weight or volume unit of the polymer is much higher than what is the case for linear polymers. Functional T groups may be used to impart a function in a material, like an antioxidant, a UV absorber, or a radical scavenger as described in WO publication No. 02092668.
Alternatively the T groups may be used as very efficient cross-linkers of organic materials like epoxy resins or polyurethanes or as cross-linkers for thermoplastics. Due to the high degree of cross-linking between dendritic polymers and such organic compounds the dendritic polymers are superior cross-linkers compared to conventional cross-linkers like polyamines, polyalcohols, or multifunctional acrylates. Higher degree of cross-linking of an organic material like a cross-linked thermoplastic improves properties such as chemical resistance, weather resistance and wears resistance and makes the material useful for applications at higher temperature. (Hans Zweifel (ed.), Plastics Additives Handbook, Carl Hanser Verlag, München, (2001), 725-811). The T groups may also be used to organize the dendritic polymers in a network. As component in a material the dendritic polymer thus may induce improved barrier properties. Alternatively such dendritic polymers may be used as a binder or as a component in a thermoset plastic.
Dendrimers are usually manufactured in relatively complicated and expensive synthesis comprising several steps. The process conditions must be maintained very accurately in order to achieve a perfect progressive branch structure. Their industrial applications are therefore limited.
A general way of manufacture of hyper branched polymers was early described by Flory (P. J. Flory, Principles of Polymer Chemistry, Cornell University, (1953)). The polymerization of an AB2 monomer where A may react with B but where the reactions between A and A and between B and B are precluded, leads to a hyperbranched polymer.
Another way of manufacturing hyperbranched polymers involves the utilization of a reactive monomer that also carries an initiator, a so-called “inimer”. One example is the base catalyzed reaction between the inimer glycidol and the germ trimethylol propane as illustrated by Formula 2.
FORMULA 2K germ (the beginning of the polymer molecule)L linear propagationD dendritic branchingT termination (the end of the polymer molecule)
Hyperbranched polymers made in this way have properties that are quite similar to corresponding dendrimers (A. Sunder, R. Hanselmann, H. Frey, R. Mühlhaupt; Macromolecules, (1998), 32, 4240). This implies a much lower viscosity than that of linear polymers with a comparable number of free available HO-groups. A characteristic feature in the manufacturing process is that the inimer glycidol must be added very slowly to the germ and in a very thin dilution. Thus, the cost-efficiency of the process is severely reduced which is why the utility of hyperbranched polymers in industrial applications is quite limited.
It is previously known to perform certain modifications of the T groups of hyperbranched polymers. J.-P. Majoral, A.-M. Caminade and R. Kraemer, Anales de Química Int. Ed., (1997), 93, 415-421 describe the functionalization of dendrimers containing phosphorus. The functionalization of the T groups can be made with identical/similar chemical groups or with different chemical groups.
FR 2761691 discusses dendrimers with functional groups at the surface that are modified through a reaction with cyclic thioesters. The reaction leads to a dendrimer surface with thiol groups that are attached to the dendrimer by amide or amine bondings. The products may be used as antioxidants. The dendrimers described are of the type polyamidoamine dendrimers (PAMAM dendrimers). PAMAM dendrimers contain tertiary amines that comparatively easy may be degraded after conversion to quaternary ammonium salts or aminoxides (A. W. Hofmann, Justus Liehigs Ann. Chem. (1851), 78, 253-286; A. C. Cope, E. R. Trumbull, Org. React. (1960), 11, 317-493; A. C. Cope, T. T. Foster, p. H. Towle, J. Am. Chem. Soc. (1949), 71, 3929-3935). Quaternary ammonium salts or aminoxides from amine based dendrimers can be formed when additives of amine based dendrimers are incorporated/compounded into thermoplastics with subsequent processing of the thermoplastics (e.g. film blowing, extrusion, casting). Such a degradation on one hand leads to a partial deterioration of the dendrimer core and on the other hand to formation of degradation products which may leak out and thereby reduce the surface quality of the polymer product. In addition tertiary amines may during processing of the thermoplastic form free radicals by decomposition of hydro peroxides (A. V. Tobolsky, R. B. Mesrobian, Organic Peroxides, (1954), Interscience Publishers, New York, p. 104-106). Dendrimers and hyperbranched polymers that contain tertiary amines thereby may induce an unintended degradation of thermoplastics during their processing, storage or use.
WO 01/48057 discusses multifunctional stabilizers against thermal oxidative degradation based on a core structure containing tertiary amines. As mentioned above this may lead to an unintended degradation of the core structure during processing, storage or use of (the) thermoplastics. The molar weight of a typical stabilizer manufactured in accordance with WO 01/48057 is 1246 g/mole.
WO 97/19987 discusses combinations of polymer additives and modified dendrimers that may be used in polymer materials. In the exemplification of WO 97/199987 the dendrimers are based on polypropyleneimine (PPI) of 3rd, 4th and 5th generation thereby including 16, 32, and 64 terminal amine groups. The core structure contains tertiary amines which may lead to an unintended degradation of the core structure during processing, storage or use of thermoplastics. The modification of the PPI dendrimer with a fatty acid to form a multifunctional fatty acid amide may bee conducted by means of heating in a suitable solvent. The tertiary amine groups in the core structure of the dendrimer and primary amine groups at the dendrimer surface may in presence of oxygen contribute to partial degradation of the dendrimer structure. As explained above free radicals may be formed by decomposition of hydro peroxides. Such a partial degradation is indicated by a faint brown or yellow colour of the modified PPI dendrimer, like in examples I, XI, and XII in WO 97/19987. Typical molecule weights for modified PPI dendrimers in WO 97/19987 are in the range 10 000 to 40 000 g/mole. In WO 02/092668 surface activated hyperbranched or dendritic stabilizers comprising at least one additive group and a hyperbranched or dendritic core is discussed. In the exemplification of WO 02/092668 only dendritic cores based on 2,2-bis-(hydroxymethyl)-propionic acid is used. The dendritic core and the bonding to the additive group thereby are mainly based on ester bondings, which make the stabilizer sensitive to hydrolysis. In addition the exemplification of WO 02/092668 shows that the molecules of the prepared stabilizers as determined by gel permeation chromatography is between 1000 and 1500 grams/mole.
One type of particulate polymers with properties corresponding to the properties of hyperbranched polymers comprises an inorganic SixO(1.5)x-core with one T group per Si atom and is known as POSS (polyhedral oligosilesquioxanes). The most common compound of this class is a POSS with x=8 and substantially cubic structure (C. Sanchez, G. J. de A. A. Soler-Illia, F. Ribot, T. Lalot, C. R. Mayer, V. Cabuil; Chem. Mater., (2001), 13, 3066). The manufacture of POSS is expensive (M. C. Gravel, C. Zhang, M. Dinderman, R. M. Laine; Appl. Organometal. Chem., (1999), 13, 329-336 and WO 01/10871) and their industrial applicability is therefore limited.
Another type of particulate polymers with properties corresponding to the properties of hyperbranched polymers consists of an inorganic SixO(1.5)x core that carries one T group per Si atom and may be manufactured in a sol-gel process through controlled hydrolysis and condensation of a silane with a structure:X—B—Si(—Y)3 
Where Y is chosen among hydrolysable residues and X—B basically corresponds to the T group. The process is described e.g. in Applicant's own WO publication No. 0208343. Sol-gel processes may be cost efficient so that they may be conducted in industrial scale from favourable raw materials and under mild conditions, i.e. without use of high pressures or high temperatures and without particular precautions like extreme dilution or the like. Thus particulate polymers with properties corresponding to properties of hyperbranched polymers manufactured by sol gel processes are industrially applicable in many areas.
Many examples of utilization of sol gel products in polymer products are known (DE 199 33 098, EP 666 290). Normally the main focus is placed upon the inorganic SixO(1.5)x core with a size in the nanometer range and thereby upon the sol-gel product as inorganic nano particle, cf. DE 199 33 098 and EP 486 469. The inorganic residues X—B are typically used to anchor the sol gel products in an organic matrix, cf. EP 486 469.
The sol gel process involving hydrolysis and condensation of a silane in which the X—B group contains one or more amide groups is particularly simple because no external catalyst is needed and because the process may be conducted at ambient temperature or under moderate heating. One example is controlled hydrolysis and condensation of γ-aminopropyl trialkoxysilane as described in applicant's own patent application, WO publication No. 0208343. Controlled hydrolysis and condensation of silanes in which the X—B groups contains one or more amide groups typically leads to a sol in which the resulting particulate polymer product has an organic/inorganic structure (hybrid polymer) that is comparable with a hyperbranched polymer product with a number of more or less free amine groups in the T groups. Such organic/inorganic hybrid polymers exhibits a large number of functional T groups compared to their weight and/or volume. At the same time its compact structure compared to the structure of linear polymers ensures desirable properties like low viscosity and good admixing properties with thermoset plastics and thermoplastics. An example of an organic/inorganic hybrid polymer with properties corresponding to a hyperbranched polymer is shown by Formula 3:
FORMULA 3D = dendritic branching based on SiO1.5T termination (functional T-groups)D-groups that are bonded to fewer than three D units do not carry hydrolysed and/or condensed substituents
Use of fat-soluble metal compounds in which the metal is present in its highest stable oxidation state at standard conditions and/or organic/inorganic hybrid polymers with properties similar to hyperbranched polymers can improve the compatibility between different thermoplastics. In addition polymer compositions, e.g. in the form of compounds comprising at least one polyolefin and at least one of the following components                a) a thermoplastic which is not a polyolefin,        b) hyperbranched organic/inorganic hybrid polymer comprising an inorganic core carrying an organic branches, core and branches forming a particle structure,        c) fat-soluble metal compound in which the metal is present in its highest stable oxidation state at standard conditions (25° C. and maximum 98% humidity)in addition to known polymer additives (Hans Zweifel (ed.), Plastics Additives Handbook, Carl Hanser Verlag, München, (2001)) can be used in applications other than that of pure thermoplastic materials including compositions thereof.Objects        
It is an object of the present invention to provide polymer compositions comprising at least one polyolefin, for which properties like weather resistance, scratch resistance, viscosity, degree of cross-linking, shelf life, barrier properties, flame and temperature resistance, rigidity, retention of additives and/r degradation products, and controlled release of additives easily can be adapted in dependence of the relevant application.
The Invention
The above mentioned objects are achieved by means of a polymer composition as claimed in claim 1.
According to another aspect the invention concerns use of such a polymer compositions, as claimed in claims 17-19.
Preferred embodiments of the invention are disclosed by the dependent claims.
The difference between the methods of manufacture of the polybranched organic/inorganic hybrid polymers defined by claims 2 and 12 respectively solely depends on whether the starting organic amino-functional silanes used are hydrolysed and condensed or not hydrolysed. In the latter case hydrolysis and condensation form the first step in a process comprising at least two steps. In the former case such a step obviously is redundant and therefore omitted. The skilled artisan will furthermore understand that the group X—B is chosen such that it will not be hydrolysed under the conditions that will be applied for the method.
In either case free amine groups are modified through a chemical substitution after the completed silane hydrolysis and condensation. Suitable chemical substitutions are conducted between the free amine groups in the T groups and reactive compounds that preferably react actually quantitatively with more or less free amine groups at temperatures typically below 470 K and pressures typically lower than 0.3 MPa.
Particularly interesting are sol-gel processes by which the T groups may be chemically modified in one or more steps immediately after the hydrolysis and condensation has been completed and for which the reactor equipment used for the silane hydrolysis and condensation may be employed. Such batch processes form the basis for a very cost efficient manufacture of particulate organic/inorganic polybranched polymers which can carry a large number of different T groups and which therefore may be used in a large number of different industrial areas of application.
By reactions typical for primary and secondary amines is meant addition reactions, substitution reactions and combinations of such reactions with suitable reactant such as, but not limited to, compounds comprising epoxy groups, isocyanate groups, reactive double bonds, substitutable groups, and proton donating groups.
By an alternative or supplementary modification an acid is added, which may be a Lewis acid or a Broensted acid, and which is able to cause an addition to N atoms in the X—B group in order to convert such N atoms to quaternary nitronium ions.
By controlled hydrolysis and condensation in this description is understood hydrolysis and condensation of a silane compound as described in WO publication No. 0208343 with the difference that the reaction mixture includes a suitable stabilizer that prevents oxidative degradation of reactants and reaction products during hydrolysis and condensation and subsequent modification.
The first step is hydrolysis of a suitable silane compound, R′—Si(OR)n, wherein the group R′ does not participate in the hydrolysis or condensation reactions. Alkoxide ligands are replaced by hydroxyl groups:Si—OR+H—OH Si—OH+ROH
A controlled amount of water and a controlled amount of a glycol based solvent is added during this step. The reaction temperature and the reaction time are also controlled.
The second step is condensation in which the hydroxyl group can react with hydroxyl groups or alkoxy groups from other silicon centres and form Si—O—Si bonds and water or alcohol respectively:Si—OH+HO—Si Si—O—Si+H2OorSi—OR+HO—Si Si—O—Si+ROH
To manufacture particles of a certain size it is required to establish chemical conditions that ensures a correct balance between the kinetics of the two reactions, namely condensation and hydrolysis. While the condensation contributes to formation of polymer chains from (single) monomer molecules, the hydrolysis contributes to a polycrystallinic precipitation or oxohydroxide precipitation. The combination of amino-functional silanes and exchange of alkoxide groups with strong ligands will moderate the hydrolysis reaction, which will ensure that the polymer chains not become too long but remain in the size of oligomers. In practice the particles will be prepared with a size of few nanometers, more typically less than 10 nm. A suitable stabilizer is normally added to the reaction composition to avoid oxidative degradation of reactants and reaction products during hydrolysis and condensation and subsequent modification. The resulting solution is comprised of inorganic polymer particles dispersed in a solvent.
According to the present invention component d) of the composition may be manufactured by a sol-gel process comprising at least two steps in a defined chronological sequence. In the first steps the core is prepared by controlled hydrolysis and condensation of a silane with formula:X—B—Si(—Y)3 with the provisions and definitions stated in claim 4.
In the second step the organic branches is developed by a substitution of N—H hydrogen atoms of the X—B group through reactions that are typical for primary and secondary amines and/or by the alternative modification mentioned above. In the first mentioned type of reactions suitable reactants are reactive compounds such as epoxides, cyclic and non-cyclic acid derivatives, blocked and unblocked isocyanates, compounds with reactive double bonds, aldehydes, ketones, proton donating compounds, and compounds R—X that comprises                a) a suitable atom or atom group X and a group R,in which R—X may react with more or less free amine groups in a substitution reaction in which an atom or an atom group X is replaced by an amine group (Endre Berner, “Laerebok i organisk kjemi”, Aschehoug & Co., Oslo (1964), s. 144-147) and where the group R is chosen among non-substituted saturated or unsaturated C1-C24 alkyl, substituted saturated or unsaturated C1-C24 alkyl, non-substituted or substituted aryl, aliphatic or aromatic carbonyl, while the carbon chains of said compounds optionally can contain one or more of the elements oxygen, nitrogen, sulphur, phosphorous, silicon, and boron; or groups chosen among condensation products or addition products of one or more types of chemical compounds such as acids, alcohols, phenols, amines, aldehydes, or epoxides in which the atom or atom group X preferably is chosen among halogen, substituted or non-substituted alkoxyl, phenoxyl, amine, carboxylate, sulphonate, sulphinate, phosphonate, or phosphinate.        
When step i) is an addition reaction it is convenient and preferred that this is conducted by substitution of the N—H hydrogen atom with ant A-=B double bond where A, B are chosen among the elements C, O, N, S and P. According to an also preferred alternative the addition reaction involves ring opening of an epoxide group that optionally may be succeeded by reaction (substitution) with a ketone or an aldehyde. Yet another preferred embodiment for the accomplishment of the addition reaction consists in a reaction at the N—H hydrogen atom with a blocked or unblocked isocyanate. Still another preferred embodiment for accomplishing the addition reaction includes ring opening of a cyclic acid anhydride or derivative thereof, such as a carbonic acid derivative. Also a combination of such reactant as mentioned above may be used for the desired addition reaction.
For some objects is preferred that the developed branches in the organic/inorganic hybrid polymers includes groups that are derivatives of 2,2,6,6-tetramethylpiperidine or derivatives of phenol.
When using an addition reaction a molar excess of the reactant causing the addition reaction may be added if desired, leading to repeated addition reactions which in practice involves a polymerization of the organic branches.
As reactant when using at least one substitution reaction in step i) a mono functional carboxylic acid or a derivative of a sulphinic or sulphonic acid may be used.
In step ii) the acid used can be a Lewis acid or a Broensted acid.
The method of manufacture according to the invention is not dependent upon a certain type of reaction medium and may be conducted in both aqueous and organic based dispersion agents. It is particularly surprising and beneficial that it is also applicable in water based media, which is also environmentally favourable. Presence of the organic/inorganic hybrid polymer may stabilize the polymer composition and may act to cross-link polymer chains in the composition.
For particular purposes it is preferred to use particularly selected reactants that lead to specific properties for the particulate, polybranched, organic/inorganic hybrid polymer. For example, in order to obtain a product with flame retardant properties it is advantageous to use reactants that comprise halogen for the reaction exemplified as addition reaction or substitution reaction. If a particularly hydrophobic end product is desired it may be advantageous to use at least one fluorinated reactant in step i) and/or ii) of the method according to the invention.
For further use or treatment of the particulate, polybranched organic/inorganic hybrid polymer it is convenient that it has at least one polymerizable double bond, such as part of an acryl group, vinyl group or an unsaturated fatty acid.
Examples of suitable epoxides for an addition reaction are monoglycidyl compounds that may be represented by:
where R1 is chosen among groups like hydrogen, non-substituted saturated or unsaturated C1-C24 alkyl, substituted saturated or unsaturated-C1-C24-alkyl, substituted or non-substituted aryl, aliphatic or aromatic carbonyl, in which the carbon chains of said compounds optionally may contain one or more of the elements oxygen, nitrogen, sulphur, phosphorous, silicon, and boron or where R1 is chosen from condensation products or addition products of one or more type of chemical compounds such as acids, alcohols, phenols, amines, aldehydes or epoxides.
Examples of suitable epoxides include compounds with epoxidized C═C double bonds that may be represented by:
where R1-R4 are chosen among groups like hydrogen, non-substituted saturated or unsaturated C1-C24 alkyl, substituted saturated or unsaturated C1-C24 alkyl, substituted or non-substituted aryl, aliphatic or aromatic carbonyl, in which the carbon chains of said compounds optionally may contain one or more of the elements oxygen, nitrogen, sulphur, phosphorous, silicon, and boron or where R1 is chosen from condensation products or addition products of one or more type of chemical compounds such as acids, alcohols, phenols, amines, aldehydes or epoxides.
Examples of reactive double bonds are A=B double bonds where A, B are chosen among the elements C, O, N, S and P.
Examples of acid derivatives are:
Derivatives of carboxylic acids Derivatives of suiphonic acids Derivatives of suiphinic acids Cyclic acid derivatives n = 0–10 Y = O, S, N—R1 Carbonic acid derivatives Y = O, S, N—R1, Z = O, S, N—R1 Cyclic acid anhydrides and corresponding derivatives n = 0–10 Y = O, S, N—R1 Cyclic carbonic acid derivatives n = 0–10 Y = O, S, N—R1, Z = O, S, N—R1
Where R1 is chosen among groups like hydrogen, non-substituted saturated or unsaturated C1-C24 alkyl, substituted saturated or unsaturated C1-C24 alkyl, substituted or non-substituted aryl, aliphatic or aromatic carbonyl, in which the carbon chains of said compounds optionally may contain one or more of the elements oxygen, nitrogen, sulphur, phosphorous, silicon, and boron or where R1 is chosen from condensation products or addition products of one or more type of chemical compounds such as acids, alcohols, phenols, amines, aldehydes or epoxides and X is a suitable exit group such as halogen, substituted or non-substituted alkoxy, phenoxy, amine, carboxylate, sulphonate, sulphinate, phosphonate, or phosfinate.
Examples of suitable isocyanates may be represented by:

Where R1 is chosen among groups like hydrogen, non-substituted saturated or unsaturated C1-C24 alkyl, substituted saturated or unsaturated C1-C24 alkyl, substituted or non-substituted aryl, aliphatic or aromatic carbonyl, in which the carbon chains of said compounds optionally may contain one or more of the elements oxygen, nitrogen, sulphur, phosphorous, silicon, and boron or where R1 is chosen from condensation products or addition products of one or more type of chemical compounds such as acids, alcohols, phenols, amines, aldehydes or epoxides and where the isocyanate group my be blocked by means of known chemical substances.
Examples of suitable aldehydes and ketones may be represented by:
Where R1 is chosen among groups like hydrogen, non-substituted saturated or unsaturated C1-C24 alkyl, substituted saturated or unsaturated C1-C24 alkyl, substituted or non-substituted aryl, aliphatic or aromatic carbonyl, in which the carbon chains of said compounds optionally may contain one or more of the elements oxygen, nitrogen, sulphur, phosphorous, silicon, and boron or where R1 is chosen from condensation products or addition products of one or more type of chemical compounds such as acids, alcohols, phenols, amines, aldehydes or epoxides.
An example of a combination of reactions is                a) substitution of N—H hydrogen atoms at the non-hydrolyzable substituent X—B group by an epoxide, resulting in the formation of an aminoalcohol,        b) substitution of the aminoalcohol by a ketone or an aldehyde resulting in the formation of an oxazolidine.        
In the manufacture of a polybranched, organic/inorganic hybrid polymer by a sol-gel process, the hybrid polymer having the form of an inorganic core and organic branches, a suitable stabilizer is normally added to the reaction composition to prevent oxidative degradation of the reactants and reaction products during hydrolysis and condensation and subsequent modification of X—B—Si(—Y)3. Suitable stabilizers are radical scavengers based on hindered amines, one or more antioxidants or a combination of same (Hans Zweifel (ed.), Plastics Additives Handbook, Carl Hanser Verlag, München, (2001), 10-19).
By first hydrolysing the molecules that comprises the organic core and thereafter through suitable reaction, addition or addition, attach the organic branches thereto, the method of the present invention thereby provides a particularly high degree of branching and a control of the particle size in the thus produced sol that has never before been achieved. This leads to several advantages. Firstly the hydrolysis may be conducted more completely than what is the case if the particle composition includes some very large particles. Secondly the risk that water used for the hydrolysis to some extent unintentionally reacts with active groups in the organic parts of the molecule is avoided.
The invention thus provide a possibility of manufacturing a large number of differently functionalized organic/inorganic hybrid polymers with properties corresponding to the properties of hyperbranched polymers, through a simple two step batch process under mild conditions (T<470 K and pressure P<0.3 MPa).
Such organic/inorganic hybrid polymers have properties that are comparable with the properties of organic, hyperbranched polymers and may be used for many applications, like functional additives in thermoplastics and thermoset plastics, e.g. as antioxidant, UV absorb or radical scavenger, as cross-binder in thermoplastics and thermoset plastics, as component in adhesives, lacquers and coating products and as functional material in other connections. Used as additive the polybranched hybrid polymers prepared according to the invention contribute to a lasting increase in scratch resistance and weather resistance for the products in which they are used.
Temperature and stability during hydrolysis of the organic/inorganic hybrid polymers according to the invention are better than those of the organic hyperbranched polymers due to stable Si—O bonds in the polymer core and due to the core's compact structure with a very high degree of cross-linking.
Reversible viscosity changes is observed during heating/cooling due to the particulate structure with a stable inorganic core and function carrying organic groups that are bonded to the inorganic core, which is important in connection with the subsequent treatment/processing of products based on the invention.
The choice of method for the manufacture of materials and products according to the invention enables an industrial utilization of the invention in a cost efficient manner. The manufacture of materials and products according to the invention is based on a batch process under mild conditions (T<470 K and pressure P<0.3 MPa) in which the raw materials are chosen among a definite group of inexpensive silanes and bulk chemicals that are used in large quantities in industrial utilizations of polymers
By convenient choice of raw materials for the method according to the invention, stabilizers, coating forming additives or other additives may be manufactured. Such stabilizers or other additives provide a broader range of applications than what is the case for known, mono functional stabilizers and may be used in lacquers, paints, thermoset plastics and thermoplastics. By convenient choice of raw materials one may for instance in combination with a suitable polymer achieve an excellent barrier layer for molecules in gas and liquid form, like water, O2, CO2 and hydrocarbons.
The invention furthermore concerns additives for avoiding leakages of additives and/or degradation products. Correspondingly self-organizing networks may be formed, such as in adhesives or thermo-stable/thermo-reversible networks that find use in functional materials.
Fat-soluble metal compounds for use in a composition according to the invention may be prepared (manufactured) by reacting a metal salt with an acidic, organic compound in a process in which a suitable oxidation agent ensures that all the metal in the end product is present in its highest stable oxidation step at standard conditions (25 C and maximum 98% humidity). The acidic, organic compound can e.g. be a C8-C24 fatty acid or a C8-C24 fatty acid derivative. A particular feature of the manufacturing process can involve the use of a completely or partially halogenated C8-C24 fatty acid or derivative thereof. Another particular feature of the manufacturing process can be that the C8-C24 fatty acid or C8-C24 fatty acid derivative is completely or partially unsaturated. A third particular feature of the manufacturing process can be that the oxidation agent used is hydrogen peroxide or an organic peroxide.
Per se known polymer additives are described by Hans Zweifel (Hans Zweifel (ed.), Plastics Additives Handbook, Carl Hanser Verlag, München, (2001)).
The polymer composition according to the invention may have the form of an independent, homogenous product, i.e. that all the components are evenly distributed in a polymer matrix. The polymer composition may also constitute a layer of a laminate in which the other layers may have a composition that either fall within or not fall within the definition of the polymer composition according to the invention. In cases where the other layers do not fall within the definition according to the invention, these layers may be polymers of one or more components or substrates of another type, i.e. not polymers. The polymer composition may also have the form of a tube that either is a complete product or constitutes a protecting film around other components that similar to the layers of the laminate structure either may fall within or not fall within the definition of the polymer composition according to the present invention.
With “partially heterogeneous structure” inn this context is understood a product that does not have a uniform structure throughout but may have a composition in the form of a laminate in which each layer is homogenous but different from the composition of at least one other layer.
The polymer composition may, however, also have a heterogeneous structure (product) in which each layer separately do not fall within the definition of the present invention, but where the product as a whole still falls within the definition of the product. For example, component d) and e) may constitute a majority of one layer of the product while another layer of the product may be a pure polymer such as PE or PP.
A polymer composition according to the invention may be used as a transition (intermediate) layer between a coating based on a polybranched organic/inorganic hybrid polymer and a thermoplastic (material).